Question 23.10: Will the reaction described by the equation CO(g, 0.010 bar)......

Will the reaction described by the equation

CO(g, 0.010\ bar) + 2\ H_{2}(g, 0.010\ bar) → CH_{3}OH(l)

occur spontaneously at 25°C?

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We first use Table 23.1 to calculate ΔG^{\circ}_{rxn}:

ΔG^{\circ}_{rxn} = ΔG^{\circ}_{f}[CH_{3}OH(l)] – ΔG^{\circ}_{f}[CO(g)] –2\ ΔG^{\circ}_{f}[H_{2}(g)] \\=(1)(–166.6\ kJ·mol^{–1}) – (1)(–137.2\ kJ·mol^{–1}) –(2)(0\ kJ·mol^{–1}) \\= –29.4\ kJ·mol^{–1}

The negative value of ΔG^{\circ}_{rxn} means that the reaction described by the equation

CO(g, 1\ bar) + 2\ H_{2}(g, 1\ bar) → CH_{3}OH(l)

proceeds spontaneously at standard conditions. However, it does not tell us whether the reaction will occur when the pressures of CO(g) and H_{2}(g)  both are 0.010 bar, as originally stated. To find out, we must use Equation 23.20 to calculate ΔG_{rxn}

ΔG_{rxn} =ΔG^{\circ}_{rxn}+ RT\ ln\ Q \\ = –29.4\ kJ·mol^{–1} + (8.3145\ J·K^{–1}·mol^{–1})(298\ K)ln\left(\frac{1}{(0.010)(0.010)^2 } \right) \\=–29.4\ kJ·mol^{–1} + 34.2\ kJ·mol^{–1} = +4.8\ kJ·mol^{–1}

Because ΔG_{rxn} \gt 0, the reaction will not occur spontaneously if the pressures of CO(g) and H_{2}(g) are 0.010 bar, even though the reaction is spontaneous at standard conditions.

TABLE 23.1 Standard molar entropies (S°), enthalpies of formation (\Delta H^{\circ}_{f} ), and Gibbs energies of formation (\Delta G^{\circ}_{f} ) of various substances at 25°C and one bar (see also Appendix D)*
Substance S^{\circ}/J\cdot K^{−1}\cdot mol^{−1} \Delta H^{\circ}_{f}/kJ\cdot mol^{-1} \Delta G^{\circ}_{f}/kJ\cdot mol^{-1} Substance S^{\circ}/J\cdot K^{−1}\cdot mol^{−1} \Delta H^{\circ}_{f}/kJ\cdot mol^{-1} \Delta G^{\circ}_{f}/kJ\cdot mol^{-1}
Ag(s) 42.6 0 0 H_{2}O_{2}(l) 109.6 –187.8 –120.4
AgCl(s) 96.3 –127.0 –109.8 H_{2}S(g) 205.8 –20.6 –33.4
C(s,\ diamond) 2.4 1.9 2.9 N(g) 153.3 472.7 455.5
C(s,\ graphite) 5.7 0 0 N_2(g) 191.6 0 0
CH_{4}(g) 186.3 –74.6 –50.5 NH_{3}(g) 192.8 –45.9 –16.4
C_{2}H_{2}(g) 200.9 227.4 209.9 N_{2}H_{4}(l ) 121.2 50.6 149.3
C_{2}H_{4}(g) 219.3 52.4 68.4 NO(g) 210.8 91.3 87.6
C_{6}H_{6}(l) 173.4 49.1 124.5 NO_{2}(g) 240.1 33.2 51.3
CH_{3}OH(l ) 126.8 –239.2 –166.6 N_{2}O(g) 220.0 81.6 103.7
CH_{3}Cl(g) 234.6 –81.9 –58.4 N_{2}O_{4}(g) 304.4 11.1 99.8
CH_{3}Cl(l ) 145.3 –102 –51.5 N_{2}O_{5}(s) 178.2 –43.1 113.9
CH_{2}Cl_{2}(g) 270.2 –95.4 –68.8 Na(g) 153.7 107.5 77.0
CH_{2}Cl_{2}(l ) 177.8 –124.2 –70.0 Na(s) 51.3 0 0
CHCl_{3}(g) 295.7 –102.7 6.0 O(g) 161.1 249.2 231.7
CHCl_{3}(l) 201.7 –134.1 –73.7 O_{2}(g) 205.2 0 0
CO(g) 197.7 –110.5 –137.2 P(s, white) 41.1 0 0
CO_{2}(g) 213.8 –393.5 –394.4 P(s, red) 22.8 –17.6 –12.1
Cl(g) 165.2 121.3 105.3 PCl_3(g) 311.8 –287.0 –267.8
Cl_{2}(g) 223.1 0 0 PCl_5(g) 364.6 –374.9 –305.0
H(g) 114.7 218.0 203.3 S(s, rhombic) 28.5 0 0
H_{2}(g) 130.7 0 0 S(s, monoclinic) 32.6 0.3 0.1
H_{2}O(g) 188.8 –241.8 –228.6 SO_{2}(g) 248.2 –296.8 –300.1
H_{2}O(l) 70.0 –285.8 –237.1 SO_{3}(g) 256.8 –395.7 –371.1
*Most data from CRC Handbook of Chemistry and Physics, 87th Online Edition, 2006–2007.

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